CN106832068B - A kind of method that modified polyacrylonitrile resin prepares novel antibacterial material - Google Patents
A kind of method that modified polyacrylonitrile resin prepares novel antibacterial material Download PDFInfo
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- CN106832068B CN106832068B CN201611143961.3A CN201611143961A CN106832068B CN 106832068 B CN106832068 B CN 106832068B CN 201611143961 A CN201611143961 A CN 201611143961A CN 106832068 B CN106832068 B CN 106832068B
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- polyacrylonitrile
- degrees celsius
- polyacrylonitrile resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
Abstract
The invention discloses a kind of polymer materials using the preparation of itrile group click chemistry modified polyacrylonitrile resin with strong antibiotic property, itrile group is modified by addition sodium azide and silver nitrate at a certain temperature and is prepared after 80-140 degrees Celsius of reaction a period of time to staphylococcus aureus, Escherichia coli, drug resistance enterococcus, drug-resistant pseudomonas aeruginosa various bacteria has the modified material of anti-microbial property, preparation process is easy to operate, products pure, and raw material is cheap.
Description
Technical field
Novel antibacterial tree is prepared using itrile group click chemistry modified polyacrylonitrile resin is simple and quick the present invention relates to a kind of
The method of rouge, belongs to functional polymer material field.
Background technique
In recent years, with the continuous continuous improvement accelerated with industrialized level of urbanization process, society is to new material
Demand it is increasingly cumulative.Polyacrylonitrile (polyacrylonitrile, PAN) is with good stability and mechanicalness, is one
The important precursor high molecular material of kind, while possessing excellent physics and chemical property.And silver is used as a kind of effective fungicide,
With very strong bactericidal effect.Silver ion, nano silver etc. have strong permeability, safe and non-toxic, strong bactericidal, broad spectrum antibacterial simultaneously
And can also effectively facilitate damaged cell repairs regeneration, there are also the healings that can promote wound.The antibacterial applications range of nano silver
More extensively, wide prospect is opened for antibacterial cause.Such as it is used for information industry, ecological environment, daily necessities, medicine
Dressing etc..Wherein in our common baby products, milk products and tableware are exactly nano silver, while it is also safe material.
The advantages of the advantages of Polymer/nano silver composite material combines polymer and nano silver.Have become at present it is a kind of efficiently and
Functional material with development potentiality, thus how using polymer and silver it is compound prepare new and effective anti-biotic material by
The extensive research and exploration of researchers.
Currently, polymerisation in solution and emulsion polymerization, which have become, is synthetically prepared one of strong means of polyacrylonitrile resin.
System viscosity is low in solution polymerization process, heat of polymerization be easy export, heat dissipation and easy temperature control system, product relative molecular mass and point
Cloth is more stable, lower production costs；Polymerization rate is fast in emulsion polymerization process, and molecular weight is high, and heat of polymerization is easily spread, and gathers
Conjunction reaction temperature is easy to control, and polymerization system is very low phase viscosity after the reaction, thus is also suitable for preparing the polymerization of high viscosity
Object；With water as medium, production safety and reduce environmental pollution.Then polymer and silver ion can be made multiple using itrile group click chemistry
It closes and is modified, make it have anti-microbial property.Therefore, by the existing theoretical and synthetic technology of free radical polymerization, novel antibacterial is expanded
Property polyacrylonitrile material, is the new issue that macromolecule worker faces.
The invention patent utilizes itrile group click chemistry method to poly- third after preparing polyacrylonitrile resin by free radical polymerization
Alkene nitrile resin is modified, and at high temperature under the catalysis of silver nitrate, polyacrylonitrile moiety itrile group is with azido group reactive moieties
Group is converted to tetrazole silver, to prepare the modified polyacrylonitrile resin with anti-microbial property.
Summary of the invention
It is an object of the present invention to provide a kind of methods that modified polyacrylonitrile prepares novel antibacterial material.
In order to achieve the above objectives, specific technical solution of the present invention is that one kind clicks technology by free radical polymerization and itrile group
The polymerization system of the modified polyacrylonitrile of strong antibiotic property is prepared, it is characterized in that: polymerisation in solution or the homemade of emulsion polymerization are gathered
Acrylonitrile resin is dissolved into solvent, and sodium azide is added in system, and silver nitrate passes through nitrile-group modification reaction one at a certain temperature
Preparation has the modified material of anti-microbial property after the section time；
Wherein in mass ratio, polyacrylonitrile resin: sodium azide: silver nitrate=20 ~ 1000:1:1 ~ 10；
The polyacrylonitrile molecular weight: 10,000 ~ 200,000；
The solvent: n,N-Dimethylformamide, dimethyl sulfoxide；
The temperature: 80-140 degrees Celsius；
The reaction time: between 30 minutes to 96 hours；
The bacterium: staphylococcus aureus, Escherichia coli, drug resistance enterococcus, drug-resistant pseudomonas aeruginosa；
Therefore, the above-mentioned modified polypropene system preparation of claimed application has high-efficiency antimicrobial performance anti-biotic material
Method, comprising the following steps:
1. preparing reaction system according to formula described above；
2. the anti-microbial property of modified material is investigated.
In above-mentioned technical proposal, anti-microbial property can be improved by adjusting ratio.
Due to the above technical solutions, the present invention has the following advantages over the prior art: 1. present invention are using certainly
Strong antibiotic property polyacrylonitrile silverskin is synthesized by base polymerization and itrile group click chemistry technology, and is used as anti-biotic material, to medicine
The pathogen of property has comprehensive anti-microbial property, such as staphylococcus aureus, Escherichia coli, drug resistance enterococcus, drug resistance green pus bar
Bacterium, 2. present invention are easy to operate using reaction system preparation process, and products pure, raw material is cheap, substantially increase product quality,
Easily realize industrialization, 3. present invention provide theoretical foundation for design, the synthesis of the high functional high molecule material of anti-microbial property.
Specific embodiment
The following detailed description of the present invention and provide several case study on implementation:
Embodiment one: polyacrylonitrile resin is prepared by free radical polymerization.Wherein polymerisation in solution, in clean three-necked bottle
In, 10 milliliters of acrylonitrile are sequentially added, 30 milliliters of n,N-Dimethylformamide is eventually adding initiator A IBN, protects in nitrogen
It protects under atmosphere, is placed in 12 hours of polymerization in 60 DEG C of water-bath, gained is dissolved in after n,N-Dimethylformamide and is poured into largely
In methanol, white depositions are obtained, product is washed with deionized water simultaneously drying and processing, polyacrylonitrile can be obtained.Lotion is poly-
It closes, 5 milliliters of acrylonitrile and 5 milliliters of hexadecanes is uniformly mixed into oily phase respectively, by 0.5 gram of emulsifier sodium lauryl sulfate
Deionized water with 20 milliliters is uniformly mixed into water phase, is then mutually slowly added to oil in water phase under magnetic agitation effect,
Continue stirring and forms thick lotion after five minutes.Under the collective effect of ice-water bath and magnetic agitation, using ultrasonic cell disintegration instrument pair
Thick lotion carries out ultrasonication, forms acrylonitrile monemer miniemulsion.Resulting AN monomer miniemulsion will be prepared and be transferred to four-hole boiling flask
In, lead to nitrogen 30 minutes in 30 degrees Celsius of waters bath with thermostatic control and under the electric stirring of 400 revs/min of revolving speeds, then heats to 60 and take the photograph
After family name's degree, 50 milligrams of initiator potassium persulfates are added, simultaneously after isothermal reaction 6 hours, polyacrylonitrile can be obtained in logical nitrogen.
Example two: the preparation that technology is modified polymer, in mass ratio, monomer: sodium azide: nitre are clicked by itrile group
Sour silver=200:1:1 sequentially adds 5 grams of polyacrylonitrile, 25 milligrams of sodium azide, 25 milligrams of nitric acid in there-necked flask
Silver is added solvent and stirrer is added, and the ampoule bottle after tube sealing is placed in the magnetic force thermostatical oil bath under 120 degrees Celsius by sealing
It is reacted on schedule.After reaction, tube sealing is taken out, tube sealing is opened, is dissolved with 20 milliliters of DMF, pours into 400 milliliters
Methanol in, filtered after placing overnight, washing, be placed in 30 degrees Celsius of vacuum drying ovens and dry to constant weight.To resulting polymers into
A series of characterizations of row.
Embodiment three: 6 millimeters of * are cut into after unmodified and modified polyacrylonitrile resin is suppressed film forming on a glass
6 millimeters rectangular, and golden yellow grape ball is inoculated into fluid nutrient medium, passes through sky under being 150 revs/min, 37 degrees Celsius in revolving speed
Gas bath oscillator culture 12 hours.The Staphylococcus aureus of culture is inoculated into Staphylococcus aureus solid medium, will be cut
Being put into culture medium at 6 millimeters * 6 millimeters rectangular polymer materials comes into full contact with film with culture medium, then cultivates at 37 degrees Celsius
Incubator in cultivate 24 hours, observe inhibition zone.
Claims (1)
1. a kind of method that modified polyacrylonitrile prepares anti-biotic material, it is characterized in that: the polyacrylonitrile resin by emulsion polymerization is molten
Sodium azide, silver nitrate is added into solvent in solution, has anti-microbial property by nitrile-group modification reaction preparation at a certain temperature
Modified material；Wherein in mass ratio, polyacrylonitrile resin: sodium azide: silver nitrate=200:1:1；
The temperature: 120 degrees Celsius；
Reaction time: 30 minutes；
Bacterium: staphylococcus aureus；
The polyacrylonitrile resin preparation step of the emulsion polymerization: 5 milliliters of acrylonitrile and 5 milliliters of hexadecanes are uniformly mixed respectively
At oily phase, 0.5 gram of emulsifier sodium lauryl sulfate and 20 milliliters of deionized water are uniformly mixed into water phase, then in magnetic
Oil is mutually slowly added in water phase under power stirring action, continues stirring and forms thick lotion after five minutes；
Under the collective effect of ice-water bath and magnetic agitation, ultrasonication, shape are carried out to thick lotion using ultrasonic cell disintegration instrument
At acrylonitrile monemer miniemulsion；Resulting acrylonitrile monemer miniemulsion will be prepared to be transferred in four-hole boiling flask, in 30 degrees Celsius of constant temperature
Water-bath and lead to nitrogen 30 minutes under the electric stirring of 400 revs/min of revolving speeds, after then heating to 60 degrees Celsius, is added 50 milligrams
Simultaneously after isothermal reaction 6 hours, polyacrylonitrile can be obtained in initiator potassium persulfate, logical nitrogen；
The preparation step of the antibacterial modified material: in mass ratio, polyacrylonitrile resin: sodium azide: silver nitrate=200:1:
1, in there-necked flask, 5 grams of polyacrylonitrile, 25 milligrams of sodium azide, 25 milligrams of silver nitrate are sequentially added, solvent is added and adds
Enter stirrer, seals, the ampoule bottle after tube sealing is placed in the magnetic force thermostatical oil bath under 120 degrees Celsius and is carried out on schedule
Reaction；After reaction, tube sealing is taken out, tube sealing is opened, is dissolved, is poured into 400 milliliters of methanol with 20 milliliters of DMF, overnight
It filters, wash after placement, be placed in 30 degrees Celsius of vacuum drying ovens and dry to constant weight；By the polyacrylonitrile resin after drying in glass
On plate after compacting film forming to obtain the final product.
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| CN201611143961.3A CN106832068B (en) | 2016-12-13 | 2016-12-13 | A kind of method that modified polyacrylonitrile resin prepares novel antibacterial material |
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| CN112755788A (en) * | 2020-12-31 | 2021-05-07 | 太原科技大学 | Modified polyacrylonitrile ultrafiltration membrane, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106117401A (en) * | 2016-05-31 | 2016-11-16 | 鲁东大学 | A kind of novel method being prepared ferrocene-based polymer by controllable type polyacrylonitrile resin |
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| CN103421136B (en) * | 2013-08-01 | 2015-11-11 | 华南理工大学 | A kind of matrix polyacrylonitrile nano particle and preparation method thereof |
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| CN106117401A (en) * | 2016-05-31 | 2016-11-16 | 鲁东大学 | A kind of novel method being prepared ferrocene-based polymer by controllable type polyacrylonitrile resin |
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